JP6999085B2 - Sealant composition and outer wall - Google Patents

Description

The present invention relates to a sealing material composition and an outer wall.

Conventionally, a siding board or the like has been used for the outer wall of a detached house. In order to give excellent design to the appearance of a detached house, the surface of the outer wall may be uneven.

In the outer wall of a detached house, the siding sealing material is usually filled between the adjacent siding boards.
Like the siding board, the siding sealing material is exposed to the outside and is visible to the public, so its design is important. For example, the siding sealing material is required to have an appearance similar to that of a siding board so as not to impair the appearance of the outer wall.
Regarding the sealing material composition for an outer wall material, for example, Patent Document 1 aims to provide a sealing material composition that exhibits the basic performance required for a sealing material and has a rough surface on the surface of the cured product. At least one polymer selected from the group consisting of a modified silicone-based polymer, a urethane-based polymer, a urethane / epoxy-based polymer, a polysulfide-based polymer, and a silicone-based polymer, colloidal calcium carbonate, and an average particle size. Contains a polymer of 135 μm or more and has an average particle size of 135 μm or more and a content of 5 to 20 vol%. We are proposing a sealing material composition for outer wall materials.

Further, since the siding sealing material is placed in an outdoor environment, it is also desired to have excellent weather resistance, stain resistance and the like.
For example, Patent Document 2 describes a modified polymer having at least one crosslinkable silyl group and having the crosslinkable silyl group bonded to the terminal, for the purpose of providing a composition for a sealing material having excellent stain resistance. , A composition for a sealing material containing an amine compound having an alkyl group having 20 or more carbon atoms and an amino group 1, a silane coupling agent having an amino group 2, a filler, and a curing catalyst has been proposed. ..
In the examples of Patent Document 2, a silane coupling agent 1 [(CH ₃ O) ₃ SiC ₃ H ₆ NH ₂ )] or the like is used as the silane coupling agent having an amino group 2.

Japanese Patent No. 4682554 Japanese Unexamined Patent Publication No. 2017-190382

In recent years, in order to enhance the appearance of a detached house, for example, there is a tendency to improve the roughness of the surface of the siding board, that is, to increase the unevenness of the surface of the siding board.
Along with this, it is required to increase the unevenness of the surface of the siding sealing material in accordance with the surface of the siding board, that is, to increase the height of the convex portion on the surface of the sealing material.
However, if the convex portion on the surface of the sealing material becomes high, for example, dust is likely to be caught on the convex portion, and / or dirt due to soil, exhaust gas, etc. (for example, carbon black, etc.) is likely to adhere to the convex portion. , There is a concern that the stain resistance of the sealing material will decrease.

Under these circumstances, the present inventors prepared and evaluated a composition capable of forming irregularities on the surface of the sealing material with reference to Patent Document 1, and found that such a composition has stain resistance of the sealing material. , It became clear that the design may be poor (Comparative Example 7).
Further, when a composition having excellent stain resistance was prepared and evaluated with reference to Patent Document 2, it became clear that such a composition had poor designability (Comparative Examples 5 and 6). ..

Next, the present inventors prepared a composition capable of forming irregularities on the surface of the sealing material by combining Patent Documents 1 and 2, and evaluated the composition. As a result, such a composition is required for the outer wall in recent years. It was clarified that the stain resistance of the sealing material may be poor in addition to the case where the high designability is not satisfied (Comparative Examples 2 to 4).
In addition, when a composition capable of forming the convex portion on the surface of the sealing material higher was prepared and evaluated, it became clear that such a composition may have poor stain resistance of the sealing material (). Comparative Example 1).

Therefore, an object of the present invention is to provide a sealing material composition having excellent designability and stain resistance.
Another object of the present invention is to provide an outer wall having excellent design and stain resistance.

As a result of diligent research to solve the above problems, the present inventors have obtained results.
(A) A modified polymer having a crosslinkable silyl group at the end,
(B) An alkylamine having a melting point or a freezing point of 50 ° C. or higher and having an alkyl group having 20 or more carbon atoms.
(C) An amine-based silane coupling agent having a triethoxysilyl group and
(D) Calcium carbonate having an average particle size of 300 to 450 μm,
(E) Black silica having an average particle size of 150 to 250 μm and
(F) Filler and
(G) Plasticizer and
(H) Containing with a curing catalyst,
The content of the (B) alkylamine is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the (A) modified polymer.
The content of the (C) amine-based silane coupling agent is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the (A) modified polymer.
The content of the calcium carbonate (D) is 30 to 50 parts by mass with respect to 100 parts by mass of the modified polymer (A).
According to the composition, the content of the black silica (E) is 5 to 20 parts by mass with respect to 100 parts by mass of the modified polymer (A), and the present invention has been found to obtain a desired effect. It came to.
The present invention is based on the above findings and the like, and specifically solves the above problems by the following configurations.

[1] (A) A modified polymer having a crosslinkable silyl group at the end,
(B) An alkylamine having a melting point or a freezing point of 50 ° C. or higher and having an alkyl group having 20 or more carbon atoms.
(C) An amine-based silane coupling agent having a triethoxysilyl group and
(D) Calcium carbonate having an average particle size of 300 to 450 μm,
(E) Black silica having an average particle size of 150 to 250 μm and
(F) Filler and
(G) Plasticizer and
(H) Containing with a curing catalyst,
The content of the (B) alkylamine is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the (A) modified polymer.
The content of the (C) amine-based silane coupling agent is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the (A) modified polymer.
The content of the calcium carbonate (D) is 30 to 50 parts by mass with respect to 100 parts by mass of the modified polymer (A).
The sealing material composition, wherein the content of the black silica (E) is 5 to 20 parts by mass with respect to 100 parts by mass of the modified polymer (A).
[2] The sealing material composition according to [1], wherein the (B) alkylamine is a monoamine.
[3] The sealing material composition according to [1] or [2], wherein the (H) curing catalyst contains a tin catalyst.
[4] The sealing material composition according to any one of [1] to [3], wherein the crosslinkable silyl group has a hydrolyzable silyl group.
[5] The modified polymer (A) is a modified poly (meth) acrylate having a crosslinkable silyl group at the end and / or a modified polyoxyalkylene having a crosslinkable silyl group at the end, [1] to [4]. The sealant composition according to any one of.
[6] An outer wall filled with the sealant composition according to any one of [1] to [5].

The sealing material composition of the present invention is excellent in design and stain resistance.
Further, the outer wall of the present invention is excellent in design and stain resistance.

The present invention will be described in detail below.
In addition, in this specification, (meth) acrylate represents acrylate or methacrylate, (meth) acryloyl represents acryloyl or methacryloyl, and (meth) acrylic represents acrylic or methacrylic.
Further, the numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
In the present specification, unless otherwise specified, each component may be used alone or in combination of two or more kinds of substances corresponding to the component. When a component contains two or more substances, the content of the component means the total content of the two or more substances.
Unless otherwise specified in the present specification, each component is not particularly limited in its production method. For example, conventionally known ones can be mentioned.
Further, in the present specification, "(A) modified polymer" may be simply referred to as "(A) component" or "(A)". The same applies to (B) alkylamine, (C) amine-based silane coupling agent, (D) calcium carbonate, (E) black silica, (F) filler, (G) plasticizer and (H) curing catalyst. ..

[Sealing material composition]
The sealing material composition of the present invention (the composition of the present invention) is
(A) A modified polymer having a crosslinkable silyl group at the end,
(B) An alkylamine having a melting point or a freezing point of 50 ° C. or higher and having an alkyl group having 20 or more carbon atoms.
(C) An amine-based silane coupling agent having a triethoxysilyl group and
(D) Calcium carbonate having an average particle size of 300 to 450 μm,
(E) Black silica having an average particle size of 150 to 250 μm and
(F) Filler and
(G) Plasticizer and
(H) Containing with a curing catalyst,
The content of the (B) alkylamine is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the (A) modified polymer.
The content of the (C) amine-based silane coupling agent is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the (A) modified polymer.
The content of the calcium carbonate (D) is 30 to 50 parts by mass with respect to 100 parts by mass of the modified polymer (A).
It is a sealing material composition in which the content of the black silica (E) is 5 to 20 parts by mass with respect to 100 parts by mass of the modified polymer (A).

Since the composition of the present invention has such a structure, it is considered that a desired effect can be obtained. The reason is not clear, but it is presumed to be as follows.
The component (C) contained in the composition of the present invention has a group (for example, an amino group and / or an imino group) in which active hydrogen is bonded to a nitrogen atom. Therefore, the component (C) is considered to function as a compound that imparts stain resistance to the sealing material.
That is, in the cured product (sealing material) of the composition of the present invention, the component (C) bleeds out from the inside of the cured product to the surface (on the air side) of the cured product, and the amino contained in the component (C). The above (C) can form a solid salt on the surface of the cured product when the group or the like reacts with carbon dioxide in the air.
As described above, the solid salt formed by the component (C) and carbon dioxide is present on the surface of the sealing material, and by reducing the residual tack on the surface of the sealing material, dust and the like as described above can be removed. It is considered that dirt can be prevented from adhering to the surface of the sealing material.
Further, it is considered that the presence of the salt on the surface of the sealing material can impart a matte design to the surface of the sealing material.
Since the component (B) also has an amino group or the like, it can function as a compound that imparts stain resistance to the sealing material in the same manner as the component (C).

In addition, the component (C) has a triethoxysilyl group.
In general, ethoxysilyl groups are less reactive (eg, reactive in hydrolysis and / or condensation) than methoxysilyl groups.
Therefore, the component (C) is less likely to react with the component (A) than the amine-based silane coupling agent having a methoxysilyl group. Therefore, it is considered that the component (C) is more likely to bleed out from the sealing material than the amine-based silane coupling agent having a methoxysilyl group.
As described above, even if the surface unevenness of the sealing material obtained from the composition of the present invention becomes large and the surface of the sealing material is easily contaminated with dust or the like, the component (C) is sealed as described above. It is easy to bleed out from the material, and the components (B) and (C) react with carbon dioxide to form a salt, which reduces the residual tack on the surface of the sealant and removes dirt such as dust as described above. It can be prevented from adhering to the surface of the sealing material.
Further, according to the composition of the present invention, large irregularities can be imparted to the surface of the sealing material. Further, according to the composition of the present invention, it is considered that a matte feeling can be imparted to the surface of the sealing material.
For the above reasons, the composition of the present invention is considered to be excellent in design and stain resistance.
Hereinafter, each component contained in the composition of the present invention will be described in detail.

<< (A) Modified Polymer >>
The modified polymer (A) contained in the composition of the present invention is a polymer having a crosslinkable silyl group at the end.

(Main chain)
Examples of the main chain of the (A) modified polymer include polymers having a hydrocarbon skeleton such as (meth) acrylic polymers; polyethers.

-(Meta) Acrylic Polymer Examples of the (meth) acrylic polymer as the main chain include poly (meth) acrylate.
The repeating unit constituting the poly (meth) acrylate is not particularly limited as long as it contains a repeating unit made of a (meth) acrylic acid ester monomer. The hydrocarbon group of the ester portion of the (meth) acrylic acid ester monomer may be unsubstituted or may have a substituent.
From the viewpoint of excellent flexibility at low temperatures, the (meth) acrylic acid ester monomer can have the glass transition temperature of the (A) modified polymer or the main chain at −50 ° C. or lower (meth) acrylic acid ester. It is preferably a monomer.

The poly (meth) acrylate may further contain a repeating unit other than the repeating unit due to the (meth) acrylic acid ester monomer. The repeating unit other than the repeating unit using the (meth) acrylic acid ester monomer is not particularly limited. For example, a repeating unit with a compound having an ethylenic group can be mentioned.

-In the polyether as the main chain of the polyether, the hydrocarbon group bonded to the ether bond is not particularly limited. For example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof can be mentioned.
Examples of the polyether include polyoxyalkylene.
Examples of the polyoxyalkylene include polyoxyethylene, polyoxypropylene and the like.
The polyoxyalkylene is preferably polyoxypropylene.

<Crosslinkable silyl group>
The modified polymer (A) has a crosslinkable silyl group.
The crosslinkable silyl group can undergo a condensation reaction in the presence of moisture or the like by using a curing catalyst or the like.

Examples of the crosslinkable silyl group include a hydrolyzable silyl group. The crosslinkable silyl group can include a silanol group obtained by hydrolyzing a hydrolyzable silyl group.
Examples of the crosslinkable silyl group (hydrolytable silyl group) include hydrogen atom, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group and alkenyl. Examples thereof include a group in which at least one hydrolyzable group selected from the group consisting of oxy groups is bonded to a silicon atom.

-Hydrolyzable groups The hydrolyzable groups are excellent in stain resistance and workability (for example, the tack free time is an appropriate length. The same applies hereinafter), and thus hydrogen atoms, alkoxy groups, and acyloxys. At least one selected from the group consisting of a group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group is preferable, an alkoxy group is more preferable, and a methoxy group is further preferable.

In the hydrolyzable silyl group, 1 to 3 hydrolyzable groups can be bonded to one silicon atom.
The hydrolyzable silyl group is preferably a trialkoxysilyl group, more preferably a trimethoxysilyl group, from the viewpoint of excellent stain resistance and workability.
When one or two hydrolyzable groups are bonded to one silicon atom, the group that can be bonded to the silicon atom other than the hydrolyzable group is not particularly limited. For example, a hydrocarbon group can be mentioned.

The crosslinkable silyl group may further have a siloxane bond in addition to the hydrolyzable silyl group. The siloxane bond can be divalent or higher. When the crosslinkable silyl group further has a siloxane bond, the siloxane bond can be bonded to the main chain.
The siloxane bond is not particularly limited as long as it is —Si—O—. In the above-Si—O—, the organic group bonded to the silicon atom is not particularly limited.
Further, the siloxane bond may be polysiloxane. The polysiloxane is preferably divalent as one of the preferred embodiments.

<End>
The modified polymer (A) has the crosslinkable silyl group at the end.
The modified polymer (A) preferably has the crosslinkable silyl group at both ends from the viewpoint of excellent stain resistance and workability.

(Bundling of main chain and crosslinkable silyl group)
In the modified polymer (A), the crosslinkable silyl group can be bonded to the main chain directly or via an organic group. The organic group is not particularly limited.

(Modified poly (meth) acrylate, modified polyoxyalkylene)
The modified polymer (A) has a modified poly (meth) acrylate having a crosslinkable silyl group at the end and / or a crosslinkable silyl group at the end from the viewpoint of excellent stain resistance, workability and weather resistance. The modified polyoxyalkylene is preferable, and the modified poly (meth) acrylate and the modified polyoxyalkylene are more preferable.

When the modified poly (meth) acrylate and the modified polyoxyalkylene are used in combination as the (A) modified polymer, the mass ratio of the modified poly (meth) acrylate to the modified polyoxyalkylene (modified poly (meth) acrylate / The modified polyoxyalkylene) is preferably 30/70 to 70/30, more preferably 40/60 to 60/40, from the viewpoint of excellent stain resistance, workability, weather resistance, and physical properties.

The weight average molecular weight of the modified polymer (A) is preferably 10,000 to 50,000, preferably 15,000 to 40,000 from the viewpoint of excellent stain resistance, workability (handling), and weather resistance. More preferred.
In the present invention, the weight average molecular weight of the (A) modified polymer is a standard polystyrene-equivalent value based on a value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

<< (B) Alkylamine >>
The (B) alkylamine contained in the composition of the present invention is an amine having a melting point or a freezing point of 50 ° C. or higher and having an alkyl group having 20 or more carbon atoms.
The (B) alkylamine can function as a stain resistant agent for the sealing material.
The alkylamine (B) can be bleeded out to the surface of the sealing material after the composition of the present invention is cured to form the sealing material, and the residual tack of the sealing material can be reduced. In addition, the (B) alkylamine can impart a matte feeling to the sealing material.
Since the (B) alkylamine has an alkyl group having 20 or more carbon atoms, it is easily entangled with the (A) modified polymer, and since the melting point or freezing point is 50 ° C. or higher, the sealant is exposed to high temperature conditions. However, it is considered that the bleed-out is slow due to the fact that it is difficult to dissolve, and therefore, the component (B) can impart excellent stain resistance and / or matte feeling to the sealing material for a long period of time.

<Melting point or freezing point>
In the present invention, the melting point or freezing point of (B) alkylamine is 50 ° C. or higher.
(B) The melting point or freezing point of the alkylamine is excellent in designability (particularly imparting a matte feeling) and / or stain resistance (particularly long-term stain resistance), and from the viewpoint of reducing residual tack of the sealant. , 50-80 ° C. is preferable.
(B) The freezing point of the alkylamine can be measured according to JIS K 0065.

<Alkyl group with 20 or more carbon atoms>
The (B) alkylamine has an alkyl group having 20 or more carbon atoms.
The alkyl group may be linear, branched or cyclic. One of the preferred embodiments is that it is linear.

The number of carbon atoms of the above alkyl group is excellent in designability (particularly imparting a matte feeling) and / or stain resistance (particularly long-term stain resistance), and from the viewpoint of reducing residual tack of the sealing material, 22 to 22 to 30 is preferable.

Examples of the alkyl group include C ₂₀ H ₄₁ − (eicosyl group), C ₂₁ H ₄₃ −, and C ₂₂ H ₄₅ −.
Among them, the above-mentioned alkyl group has a high melting point or freezing point, is excellent in designability (particularly imparting a matte feeling) and / or stain resistance (particularly long-term stain resistance), and reduces residual tack of the sealing material. From this point of view, C ₂₂ H ₄₅ -is preferable.
One of the preferred embodiments is that the (B) alkylamine has one alkyl group per molecule.

<Amine>
The (B) alkylamine has an amino group (-NH ₂ ) and / or an imino group (-NH- or = NH).
The above (B) alkylamine preferably has an amino group.

The above (B) alkylamine is said to be superior in designability (particularly imparting a matte feeling) and / or designability and / or stain resistance (particularly long-term stain resistance) and reduce residual tack of the sealing material. From the viewpoint, it is preferably a monoamine, more preferably a compound having one amino group per molecule, and even more preferably C ₂₂ H ₄₅ -NH ₂ . The monoamine means that the (B) alkylamine has one amino group or an imino group per molecule.

<(B) Alkylamine content>
In the present invention, the content of the (B) alkylamine is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the (A) modified polymer.
In the present invention, when the content of the (B) alkylamine is in the above range, the design and stain resistance are excellent. In addition, the residual tack of the sealing material can be reduced, and a matte feeling can be given to the sealing material.
The content of the (B) alkylamine is superior to the design property and / or stain resistance, and is excellent in long-term maintenance of design property and / or stain resistance, and from the viewpoint of reducing the residual tack of the sealant. The amount is preferably 1.0 to 3.0 parts by mass with respect to 100 parts by mass of the modified polymer (A).

<< (C) Amine-based silane coupling agent >>
The (C) amine-based silane coupling agent contained in the composition of the present invention includes a triethoxysilyl group [(CH ₃ CH ₂ -O) ₃ -Si-], an amino group (-NH ₂ ) and /. Alternatively, it is an amine-based silane coupling agent having an imino group (-NH- or = NH).
The (C) amine-based silane coupling agent can function as a stain-resistant agent for the sealing material.
The (C) amine-based silane coupling agent can bleed out to the surface of the sealing material after the composition of the present invention is cured to form the sealing material, and the residual tack of the sealing material can be reduced. Further, the (C) amine-based silane coupling agent can impart a matte feeling to the surface of the sealing material.
Since the hydrolyzable silyl group of the (C) amine-based silane coupling agent has a mildly reactive triethoxysilyl group, it is difficult to react with the crosslinkable silyl group of the (A) modified polymer, and (C) Since the amine-based silane coupling agent is less likely to be incorporated into the network of (A) modified polymers, (C) the amine-based silane coupling agent bleeds on the surface of the sealant than the amine-based silane coupling agent having a methoxy group. It is thought that it is easy to go out.

<Amine type>
The (C) amine-based silane coupling agent has an amino group (-NH ₂ ) and / or an imino group (-NH-or = NH).
The (C) amine-based silane coupling agent is preferably excellent in designability (particularly imparting a matte feeling) and / or stain resistance, and preferably has an amino group from the viewpoint of reducing residual tack of the sealing material. , It is more preferable to have only an amino group.
The (C) amine-based silane coupling agent is excellent in designability (particularly imparting a matte feeling) and / or stain resistance, and has an amino group per molecule from the viewpoint of reducing residual tack of the sealing material. It is preferable to have one.

(Organic group)
In the (C) amine-based silane coupling agent, the triethoxysilyl group and the amino group and / or the imino group can be bonded via an organic group.
The organic group is not particularly limited. Examples thereof include aliphatic hydrocarbon groups (chain and branched) and aromatic hydrocarbon groups. Examples of the aliphatic hydrocarbon group include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a trimethylene group.

The (C) amine-based silane coupling agent is preferably aminoalkyltriethoxysilane from the viewpoint of being excellent in designability (particularly imparting a matte feeling) and / or stain resistance and reducing residual tack of the sealing material. , Γ-Aminoalkyltriethoxysilane is more preferred, and 3-aminopropyltriethoxysilane is even more preferred.

<Contents of (C) amine-based silane coupling agent>
In the present invention, the content of the (C) amine-based silane coupling agent is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the (A) modified polymer.
When the content of the (C) amine-based silane coupling agent is within the above range, the design and stain resistance are excellent. In addition, the residual tack of the sealing material can be reduced, and a matte feeling can be given to the sealing material.
The content of the (C) amine-based silane coupling agent is excellent in designability (particularly for imparting a matte feeling) and / or stain resistance, and the tack free time is an appropriate length for excellent workability and sealing. From the viewpoint of reducing the residual tack of the material, it is more preferably 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the modified polymer (A).

<< (D) Calcium Carbonate >>
The calcium carbonate (D) contained in the composition of the present invention is calcium carbonate having an average particle size of 300 to 450 μm.
In the present invention, the calcium carbonate (D) functions as an aggregate and can impart irregularities to the surface of the sealing material.
Further, when the average particle size of the calcium carbonate (D) is in the above range, the surface of the sealing material formed of the composition of the present invention has a high convex portion, and the sealing material is excellent in design.

<(D) Average particle size of calcium carbonate>
In the present invention, the average particle size of the calcium carbonate (D) is 300 to 450 μm.
The average particle size is preferably 320 to 380 μm from the viewpoint of being excellent in designability (particularly, imparting a feeling of unevenness).

In the present invention, (D) the average particle size of calcium carbonate is determined as the median diameter (d50, volume standard) based on the cumulative particle size distribution from the measured values of the particle size distribution by the laser diffraction / scattering method under the conditions of wet measurement. Can be done. As the laser diffraction type particle size distribution measuring device, SALD-3100 manufactured by Shimadzu Corporation can be used. The dispersion medium used for the wet measurement can be isopropyl alcohol, or the like.

The calcium carbonate (D) is not particularly limited except that the average particle size is 300 to 450 μm.
The calcium carbonate (D) is preferably white from the viewpoint of increasing the contrast with the uplift caused by the component (E) described later.

<(D) Calcium carbonate content>
In the present invention, the content of the calcium carbonate (D) is 30 to 50 parts by mass with respect to 100 parts by mass of the modified polymer (A).
When the content of (D) calcium carbonate is in the above range, it is excellent in designability (particularly imparting unevenness) and stain resistance.
When the content of the calcium carbonate (D) exceeds 50 parts by mass with respect to 100 parts by mass of the modified polymer (A), the stain resistance and physical properties are deteriorated.

The content of the calcium carbonate (D) is 32 with respect to 100 parts by mass of the modified polymer (A) from the viewpoint of being excellent in design (particularly imparting unevenness) and / or stain resistance and excellent in physical properties. It is preferably up to 50 parts by mass, more preferably 35 to 45 parts by mass.

<< (E) Black Silica >>
The (E) black silica contained in the composition of the present invention is black silica having an average particle size of 150 to 250 μm.
In the present invention, the black silica (E) has a smaller average particle size than the calcium carbonate (D), but can function as an aggregate and can impart small irregularities to the surface of the sealing material.
Further, since the black silica (E) is black, it exists as small black particles on the surface of the sealing material formed of the composition of the present invention, and can give an accent to the appearance of the sealing material. From the above viewpoint, the black silica (E) can contribute to the design of the sealing material (giving a small black ridge).

<(E) Average particle size of black silica>
In the present invention, the average particle size of the black silica (E) is 150 to 250 μm.
The average particle size is preferably 170 to 230 μm from the viewpoint of being excellent in design (particularly small black ridges and / or imparting a pattern).

In the present invention, the average particle size of (E) black silica can be measured by the same method as the above (D) average particle size of calcium carbonate.

<Black>
The color of the component (E) is black.
The method of changing the color of the component (E) to black is not particularly limited. For example, conventionally known ones can be mentioned.

(silica)
The black silica (E) is preferably silica particles as one of the preferred embodiments. The above-mentioned "silica grain" means that the inside of silica is a component of silica itself.
One of the preferred embodiments is that the black silica (E) does not contain a silica balloon.

As the black silica (E), for example, a commercially available color sand can be used.

<(E) Content of black silica>
In the present invention, the content of the (E) black silica is 5 to 20 parts by mass with respect to 100 parts by mass of the (A) modified polymer.
When the content of (E) black silica is in the above range, the design is excellent (small black ridges and / or the addition of patterns).
The content of the black silica (E) is 5 to 15 parts by mass with respect to 100 parts by mass of the modified polymer (A) from the viewpoint of excellent design and / or stain resistance and excellent physical properties. Is preferable.

Further, from the viewpoint that the content of (E) black silica is superior in designability (particularly, the balance of unevenness and / or the balance of black ridges or patterns with respect to the entire sealing material), the content of (D) calcium carbonate is described above. On the other hand, it is preferably 10 to 30% by mass, more preferably 15 to 25% by mass.

<< (F) Filler >>
The filler (F) contained in the composition of the present invention is not particularly limited as long as it is a filler that can be generally contained in the sealing material composition.
The filler (F) does not contain the component (D) and the component (E).

Examples of the filler (F) include calcium carbonate (however, the component (D) is excluded), talc, silica (however, the component (E) is excluded), carbon black and the like.
Of these, calcium carbonate is preferable. Calcium carbonate is not particularly limited except that the average particle size is less than 300 μm. For example, colloidal calcium carbonate, heavy calcium carbonate, light calcium carbonate and the like can be mentioned.

(F) Average particle size of the filler The average particle size of the (F) filler is preferably less than 150 μm and preferably 0.005 to 0.1 μm from the viewpoint of excellent mixing properties. ..
The average particle size of the filler (F) can be measured in the same manner as the average particle size of the component (D). As the laser diffraction type particle size distribution measuring device, SALD-7500 nano manufactured by Shimadzu Corporation can be used.

((F) Filler content)
From the viewpoint of excellent workability, the content of the filler (F) is preferably 100 to 300 parts by mass, more preferably 150 to 200 parts by mass with respect to 100 parts by mass of the modified polymer (A). preferable.

<< (G) Plasticizer >>
The (G) plasticizer contained in the composition of the present invention is not particularly limited as long as it can be generally used in the sealing material composition. For example, phthalates such as dioctylphthalate and diisononylphthalate; non-aromatic dibasic acid esters such as diisononyl adipate; aliphatic monocarboxylic acid esters; polyalkylene glycol esters; phosphoric acid esters; tri Merit Acid esters; chlorinated paraffins; process oils; polyether polyols such as polyethylene glycol and polypropylene glycol; epoxidized soybean oil; polyester and the like.

Among the above-mentioned (G) plasticizers, polyether polyols are preferable, and polypropylene glycol is more preferable, from the viewpoint of excellent workability.

((G) Content of plasticizer)
From the viewpoint of excellent workability, the content of the (G) plasticizer is preferably 25 to 100 parts by mass, more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the modified polymer (A). preferable.

<< (H) Curing catalyst >>
The (H) curing catalyst contained in the composition of the present invention is not particularly limited as long as it is a compound capable of reacting a crosslinkable silyl group or a hydrolyzable silyl group.

From the viewpoint of excellent workability, the (H) curing catalyst preferably contains a tin catalyst as one of the preferred embodiments.

The tin catalyst is not particularly limited.
Examples of the tin compound include carboxylic acid metal salts such as tin octanate, tin butanoate, tin caprylate, and tin oleate;
Dibutyltin (two butyl groups) such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin dimethoxydo, dibutyltin (triethoxysiloxy), dibutyltin oxide, dibutyltin diacetylacetonate Compound bound to tin atom);
Examples thereof include dioctyl tin dilaurate, diphenyl tin diacetate, and reaction products of dibutyl tin oxide and phthalates.

The above-mentioned (H) curing catalyst is preferably dibutyltin from the viewpoint of excellent workability, and dibutyl such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin dioleate, and dibutyltin diacetylacetonate. Tin diesters are more preferred.

(Contents of (H) curing catalyst)
The content of the (H) curing catalyst is preferably 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the (A) modified polymer from the viewpoint of excellent workability. ~ 1.0 part by mass is more preferable.

(Total content (D + E) / Total content (B + C))
The mass ratio of the total content (D + E) of the calcium carbonate (D) carbonate and the black silica (E) to the total content (B + C) of the (B) alkylamine and the (C) amine-based silane coupling agent [ (D + E) / (B + C)] is preferably 17.5 or less, preferably 10.0 to 17, from the viewpoint of excellent design and / or stain resistance, excellent workability, and reduction of residual tack. It is more preferably .2.

(Additive)
The composition of the present invention may further contain additives in addition to the above components. Examples of the additive include a polymer other than the above (A) modified polymer, a nitrogen-containing compound other than the above (B) alkylamine, a silane coupling agent other than the above (C) amine-based silane coupling agent, and a thixo-imparting agent. Examples include dehydrating agents and slimming agents.

The composition of the present invention is not particularly limited in its production method. For example, it can be produced by mixing the above-mentioned components (A) to (H) and additives that can be contained if necessary.
The composition of the present invention can be a one-component composition.

The appearance of the entire composition of the present invention is preferably, for example, a state in which a portion other than the above component (E) is white or gray, and small black particles of the above component (E) are mixed therein. It is mentioned as one of.
In the composition of the present invention, it is preferable that the portion other than the above component (E) is white.

The composition of the present invention can be used as a sealing material composition.
The base material to which the composition of the present invention can be applied is not particularly limited.
Examples of the material of the base material include glass, plastic, rubber, wood, metal, asphalt, stone, and porous members.
Examples of the shape of the base material include a rectangular shape (for example, a square shape and a rectangular shape) and / or a planar shape. The surface of the base material may have, for example, a shape and / or a color such as unevenness.
Examples of the use of the base material include an outer wall material. The outer wall material may be an outer wall panel. Specific examples of the outer wall material include a siding board.
The method of applying the composition of the present invention to the substrate is not particularly limited.

The composition of the present invention can be cured by, for example, moisture in the air. The temperature at the time of curing can be, for example, 5 to 35 ° C.

On the surface of the sealing material after curing the composition of the present invention, the ridges due to the above (D) and the ridges or patterns due to the above (E) can be recognized, for example, as follows.
The uplift due to the above (D) is larger and higher than the uplift due to the above (E).
The ridges due to (E) above appear black or gray.
When the above (E) is buried in the sealing material, the pattern by the above (E) looks black or gray.
As one of the preferred embodiments, the overall color of the sealing material is, for example, white or gray, except for the ridges and patterns due to the above (E). The overall color of the sealing material is preferably white, for example, except for the ridges and patterns due to the above (E).
Further, it is preferable that the surface of the sealing material is flat except for the ridges due to the above (D) or the ridges or patterns due to the above (E).
One of the preferred embodiments is that the surface of the sealing material has a matte feeling as a whole.

[outer wall]
The outer wall of the present invention is an outer wall filled with the sealing material composition of the present invention.

<Sealing material composition>
The outer wall of the present invention is excellent in design and stain resistance by using the sealing material composition of the present invention.
The sealing material composition used for the outer wall of the present invention is not particularly limited as long as it is the sealing material composition of the present invention (the composition of the present invention).
In the outer wall of the present invention, the "sealing material composition" includes the concept of a sealing material after the sealing material composition of the present invention is cured.

<Filling>
"Filling" generally means filling an open space (Kojien 5th edition). In the outer wall of the present invention, "filled" indicates a closed state to specify the structure or characteristics of the outer wall or the sealing material composition (sealing material).

As the outer wall of the present invention, for example, it is mentioned as one of preferable embodiments that the sealing material composition (sealing material) of the present invention is filled between a plurality of outer wall materials (for example, an outer wall panel). ..

(Outer wall material)
The outer wall material that can be used for the outer wall of the present invention is not particularly limited. For example, the same as above can be mentioned. One of the preferred embodiments of the outer wall material is a siding board from the viewpoint of being more excellent in design.
Since the outer wall of the present invention can have an integral appearance in the outer wall of the present invention, the outer wall material and the sealing material are provided so that the appearance of the outer wall material and the appearance of the sealing material composition (sealing material) are the same. One of the preferred embodiments is to select a material composition.

The method for manufacturing the outer wall of the present invention is not particularly limited. For example, a plurality of outer wall materials are installed on the surface of a building (for example, a wall or a pillar), the composition of the present invention is filled between adjacent outer wall materials (joints), and after filling, the composition of the present invention is applied. By curing, the outer wall of the present invention can be manufactured.

-Installation of outer wall material The method of installing the outer wall material on the surface of the building is not particularly limited. For example, conventionally known ones can be mentioned.
When the outer wall material has a shape and / or color such as unevenness on the surface thereof, for example, for designability, the outer wall material can be installed so that the surface faces up.
The method for manufacturing the outer wall material is not particularly limited. For example, conventionally known ones can be mentioned.
When installing the outer wall material, one of the preferred embodiments is to provide joints for filling the composition of the present invention at intervals between adjacent outer wall materials.
-Joints The width of joints (interval between adjacent outer wall materials) is not particularly limited. For example, it can be 1 to 50 mm. The width of the joint is preferably 5 to 20 mm from the viewpoint of excellent sealing performance.

-Filling of the composition of the present invention The method of filling the above-mentioned joint with the composition of the present invention is not particularly limited. For example, conventionally known ones can be mentioned.

-Curing the composition of the present invention The composition of the present invention can be cured by, for example, moisture in the air. The temperature at the time of curing can be, for example, 5 to 35 ° C.
When the composition of the present invention is cured, it can become a sealing material. The sealing material can fill joints between a plurality of outer wall materials, for example.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

<Manufacturing of composition>
Each component in Table 1 below was used in the composition (part by mass) shown in the same table, and these were mixed with a stirrer to prepare a composition.

<Evaluation>
The following evaluations were performed using each composition produced as described above. The results are shown in Table 1.

(Sample preparation)
Each composition prepared as described above was applied onto a substrate to a thickness of 10 mm and cured at 23 ° C. and 50% RH (relative humidity) for 24 hours to prepare a sample.

(Design: unevenness, black grains)
-Evaluation method The surface of the sealant of each sample prepared as described above was visually observed. The overall appearance of each of the above sealing materials was generally white.

-Evaluation criteria When the unevenness of the surface of the white sealant (same below) is remarkable, and black particles (same below) due to black silica (E) (or comparative black silica) can be clearly confirmed on the surface. Was evaluated as being extremely excellent in design (unevenness, black grains), and this was indicated as "◎".
When the unevenness was remarkable and the black grains could be confirmed to some extent, it was evaluated as having a slightly excellent design (unevenness, black grains), and this was indicated as "○".
The case where the unevenness was small or the black grains could hardly be confirmed was evaluated as having a slightly poor design (unevenness, black grains), and this was indicated as "Δ".
When there was no unevenness or when the black grains could not be confirmed at all, the design (unevenness, black grains) was evaluated as very poor, and this was indicated as "x".

(Design: Matte feeling)
-Evaluation method The matte feeling on the surface of the sealant of each sample prepared as described above was visually observed.

-Evaluation criteria When the matte feeling on the surface of the above sealing material is very excellent, this is indicated as "◎".
When the matte feeling on the surface of the sealing material was slightly excellent, this was indicated as "○".
When the matte feeling on the surface of the sealing material was slightly poor, this was indicated as "Δ".
When the matte feeling on the surface of the sealing material was very poor, this was indicated as "x".

(Comprehensive judgment of design)
In the present invention, with respect to the design property, the above-mentioned design property (unevenness feeling, black grain) and the above-mentioned design property (matte feeling) are comprehensively judged.
In the present invention, when the evaluation results of both the design property (unevenness feeling, black grain) and the design property (matte feeling) are "◎", it is evaluated that the design property is very excellent.
When the evaluation result of both the above-mentioned design property (unevenness, black grain) and the above-mentioned design property (matte feeling) is "○", or when one evaluation result is "○" and the other is "◎". It was evaluated that the case was slightly excellent in design.
Cases other than the above were evaluated as having poor design.

(Residual tack)
-Evaluation method The strength of the residual tack on the surface of the sealant of each sample prepared as described above was measured using a tack checker (product name: tackiness checker HTC-1, manufactured by Toyo Seiki Co., Ltd.).

-Evaluation Criteria When the strength of the residual tack was 0.2 N or less, it was evaluated to be very excellent in reducing the residual tack, and this was indicated as "◎".
When the strength of the residual tack was more than 0.2 N and 0.5 N or less, it was evaluated to be slightly excellent in reducing the residual tack, and this was indicated as “◯”.
When the strength of the residual tack exceeded 0.5 N, it was evaluated that the reduction of the residual tack was poor, and this was indicated as "x".
It is considered that the smaller the strength of the residual tack is, the more the salt of the component (B) and / or the component (C) is present on the surface of the sealing material.

(Stain resistance)
-Outdoor exposure test An outdoor exposure test was conducted in which each sample prepared as described above was placed outdoors for 3 months.

-Evaluation of stain resistance The stain resistance of the surface of the sealing material after the above outdoor exposure test was examined according to the Japan Sealing Material Industry Association standard JSIA 003: 2011.

-Evaluation criteria When the surface of the above sealing material was not dirty, it was evaluated as having excellent stain resistance after outdoor exposure, and this was marked as "◎".
When silica sand adhered to less than 10% of the surface of the sealing material, it was evaluated as having a slightly excellent stain resistance after outdoor exposure, and this was marked as "○".
When silica sand adhered to 10% or more and less than 20% of the surface of the sealing material, it was evaluated that the stain resistance after outdoor exposure was slightly poor, and this was indicated as "Δ".
When silica sand adhered to 20% or more of the surface of the sealing material, it was evaluated that the stain resistance after outdoor exposure was very poor, and this was marked as "x".

(Workability)
-Evaluation method Each composition produced as described above was applied on a substrate to a thickness of 10 mm and cured under the conditions of 23 ° C. and 50% RH.
The presence or absence of surface tack was confirmed by touching the tack on the surface of each composition (sealing material) on the substrate with a finger, and the time from the start of curing until the surface tack disappeared was measured.

-Evaluation criteria If the time until the surface tack disappears is 1 hour or more and 48 hours or less from the start of curing, the curing rate of the composition is within an appropriate range and it is evaluated as excellent in workability, and this is evaluated as "○". Was displayed.
When the time until the surface tack disappeared was less than 1 hour from the start of curing, it was evaluated that the curing rate of the composition was too fast and the workability was inferior, and this was indicated as "x".

The details of each component shown in Table 1 are as follows.
(A) Modified polymer 1: A polymer having a trimethoxysilyl group at both ends and having a main chain of poly (meth) acrylate. Product name SA410S, manufactured by Kaneka Corporation.
(A) Modified polymer 2: A polymer having a trimethoxysilyl group at both ends and having a main chain of polyoxypropylene. Product name SAX220, manufactured by Kaneka Corporation. The trimethoxysilyl group is directly attached to both ends of the main chain.

-(G) Plasticizer: Polyoxypropylene diol. Exenol 3020, manufactured by Asahi Glass Co., Ltd.

(F) Filler (coloidal calcium carbonate): Calfine 200, manufactured by Maruo Calcium. Average particle size 0.10 μm

-Comparative calcium carbonate: Calcium carbonate with an average particle size of 270 μm. NSK-1, made by NSK

(D) Calcium carbonate (aggregate): Calcium carbonate with an average particle diameter of 350 μm. NSK-3, made by NSK. Particle diameter 300-400 μm

(E) Black silica: Black silica having an average particle diameter of 200 μm. 67 Black, manufactured by Yamamori Civil Engineering Co., Ltd. Particle diameter 150-250 μm

-Comparative black silica: Black silica with an average particle diameter of 300 μm. 5N-1 Black, manufactured by Yamamori Civil Engineering Co., Ltd. Particle diameter 250-350 μm

-Chixo-imparting agent: Disparon # 6500, manufactured by Kusumoto Kasei Co., Ltd.-Dehydrating agent: Vinyltrimethoxysilane (trade name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.)

(B) Alkylamine 1: Behenylamine (C ₂₂ H ₄₅ -NH ₂ ). Product name Nissan Amine VB-S, manufactured by NOF CORPORATION. Melting point 60 ° C. Freezing point 55-65 ° C

-Comparative alkylamine: Hardened beef tallow propylene diamine with C _{17 H 33- (C 17 H 33 - NH-} (C ₃ H ₆ ) -NH ₂ ). Product name Asfazole 10, manufactured by NOF CORPORATION. Melting point 40 ° C.

(C) Amine-based silane coupling agent 1: 3-aminopropyltriethoxysilane ((CH ₃ CH ₂ O) ₃ SiC ₃ H ₆ NH ₂ ). Product name KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.

-Comparative amine-based silane coupling agent 1: 3-aminopropyltrimethoxysilane ((CH ₃ O) ₃ SiC ₃ H ₆ NH ₂ ). Product name KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.-Comparative amine-based silane coupling agent 2: N-2- (aminoethyl) -3-aminopropylmethyldimethoxylan. Product name KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.

・ Antiseptic: Brand name Mineral Spirit, manufactured by Nippon Oil Co., Ltd.

-(H) Curing catalyst: dibutyltin diacetylacetonate. U-202H, manufactured by Nitto Kaseisha

As is clear from the results shown in Table 1, Comparative Example 7 containing the component (B) and the component (C) had a large residual tack and poor stain resistance and design. Further, Comparative Example 7 had poor workability.
Instead of containing the component (B), the alkyl group contains a comparative alkylamine having a carbon number of less than 20 and a melting point of less than 50 ° C., and does not contain the component (C) and instead contains a trimethoxysilyl group. Comparative Example 8 containing the silane coupling agent 1 having the silane coupling agent 1 had poor stain resistance. Further, Comparative Example 8 had poor workability.
Comparative Examples 5 and 6 containing no component (D) and component (E) had poor design.
(D) Contains comparative calcium carbonate that does not contain a component and instead has an average particle size outside a predetermined range, and (E) contains comparative black silica that does not contain a component and instead has an average particle size outside a predetermined range. In addition, Comparative Examples 3 and 4 containing the comparative silane coupling agent 1 or 2 having a methoxysilyl group instead of containing the component (C) had poor design and stain resistance.
Comparative black silica containing (D) a comparative black silica having an average particle size outside a predetermined range instead of containing a component (E) and having an average particle size outside a predetermined range instead of containing a component (E). The contained Comparative Example 2 had a poor design.
Comparative Example 1 containing the silane coupling agent 1 having a trimethoxysilyl group instead of the component (C) had a slightly large residual tack and poor stain resistance.

On the other hand, the composition of the present invention was excellent in design and stain resistance.
In addition, the composition of the present invention had a small residual tack. From this, it is considered that the salt of the component (B) and / or the component (C) is present on the surface of the sealing material.
Moreover, the composition of the present invention was excellent in workability.

Claims (6)

(A) A modified polymer having a crosslinkable silyl group at the end,
(B) An alkylamine having a melting point or a freezing point of 50 ° C. or higher and having an alkyl group having 20 or more carbon atoms.
(C) An amine-based silane coupling agent having a triethoxysilyl group and
(D) Calcium carbonate having an average particle size of 300 to 450 μm,
(E) Black silica having an average particle size of 150 to 250 μm and
(F) Filler and
(G) Plasticizer and
(H) Containing with a curing catalyst,
The content of the (B) alkylamine is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the (A) modified polymer.
The content of the (C) amine-based silane coupling agent is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the (A) modified polymer.
The content of the calcium carbonate (D) is 30 to 50 parts by mass with respect to 100 parts by mass of the modified polymer (A).
A sealing material composition in which the content of the (E) black silica is 5 to 20 parts by mass with respect to 100 parts by mass of the (A) modified polymer. The sealing material composition according to claim 1, wherein the (B) alkylamine is a monoamine. The sealing material composition according to claim 1 or 2, wherein the (H) curing catalyst contains a tin catalyst. The sealant composition according to any one of claims 1 to 3, wherein the crosslinkable silyl group has a hydrolyzable silyl group. Any one of claims 1 to 4, wherein the modified polymer (A) is a modified poly (meth) acrylate having a crosslinkable silyl group at the end and / or a modified polyoxyalkylene having a crosslinkable silyl group at the end. The sealant composition according to. An outer wall filled with the sealing material composition according to any one of claims 1 to 5.